Novel substituted-polyaryl chromophoric compounds

ABSTRACT

The invention provides for novel substituted-polyaryl chromophoric compounds which desirably comprise a single diazo group, and optimally include a plurality of diazo groups. Preferably the chromophores exhibit optical nonlinear second-order properties and have unique absorption maximum and other chromophoric properties that make them useful for, among other things, muitifonctional optical switches or waveguides.

CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application is the U.S. National Stage of InternationalApplication No. PCT/US01/32490, filed Oct. 17, 2001, and was publishedin English as PCT WO 02/33005 under PCT Article 21(2). This applicationclaims the benefit of U.S. Provisional Application No. 60/241,658 filedOct. 19, 2000, and U.S. Provisional Application No. 60/263,731 filedJan. 24, 2001.

TECHNICAL FIELD OF THE INVENTION

[0002] The present invention pertains to new chromophores. The novelchromophoric compounds are substituted-aryl compounds comprising a diazolinkage. Optimally the chromophores include a plurality of linkageswhich contribute to their unique absorption maximum and chromophoricproperties, including optical nonlinear second-order properties. Thenovel optical nonlinear second-order compounds of the present inventionare optionally employed in devices such as multifunctional opticalswitches or waveguides.

BACKGROUND OF THE INVENTION

[0003] Chromophores are molecules that selectively transmit and absorbcolor by virtue of their possession of certain chemical groups (e.g.,nitrite(—NO₂), diazo(—N═N—), triphenylmethane, quinoneimine, xanthene,anthraquinone, or the like). The color of a chromophore is created by anelectronic transition between the highest occupied molecular orbital(HOMO) and the lowest unoccupied molecular orbital LUMO) present in thechromophore following absorption of incoming light. Due to theirpossession of color, chromophores can be employed in a wide variety ofdiverse applications. For instance, chromophores can be employed as“labels” or a means of detection, for example, in diagnosticapplications, forensics applications, laboratory studies, and the like.More recently, chromophores have been employed in the telecommunicationsindustry, for example, to convert light into electrical current (Shi etal., Science, 288, 119-122 (April 2000)), as components of amultifunctional optical switch or waveguide (e.g., U.S. Ser. No.09/357,201 and PCT/US00/19921), and for other uses.

[0004] These more recent applications, e.g., as an optical waveguide orswitch, use a chromophore to change or add optical properties bymodifying the backbone of a polymer. However, addition of a chromophoreto molecules other than polymers is well known and has been described inthe and Modification of a polymer backbone, and particularly a polyimidebackbone with different chromophores also is known in the art, and isdescribed, for instance, in Marder et al., Nature, 388, 845-851 (1997);Saaedeh et al., “Polyimides with a Diazo Chromophore Exhibiting HighThermal Stability and Large Electrooptic Coefficients”, Macromolecules,30 (18), 5403-5407 (1997); Yu et al., “Novel Second-Order NonlinearOptical, Aromatic and Aliphatic Polyimides Exhibiting High-TemperatureStability”, Applied Physics Letters, 66, 1050-1052 (1995); Yu et al.,“Novel Second-Order Nonlinear Optical Polyimides,” Society ofPhotooptical Instrumentation Engineers, 2527, 127-136; U.S. Ser. No.09/357,201; and

[0005] PCT/US00/19921). These modifications expand the responsiveness ofthe polyimide to different wavelengths of light Chromophoric compoundssuitable for use as an optical waveguide or switch optimally have a lowdielectric constant and include for instance, those described in U.S.Pat. No. 5,318,729; U.S. Ser. No. 09/357,201;PCT/US00/19921, and byMoylan et al. J. Am. Chem. Soc. 115, 12599-12600 (1993); Polymers forSecond-Order Nonlinear Optics, ACS Symposium Series 601, 66, (1995); andMiller et al. Chem. Mater., 6,1023-1032(1994). Despite the existence ofthese few compounds, a considerably larger inventory of photonicmaterials, preferably which exhibit second-order nonlinear optical(2^(o)-NLO) properties, and optimally which have a low dielectricconstant, are needed to meet the increasingly sophisticated demands ofthe telecommunications industry. The provision of further chromophores,especially 2^(o)-NLO chromophores, would increase the availability ofnovel, useful photonic materials. Optionally such further chromophoresalso can be employed for other applications, e.g., as labels inapplications outside the telecommunications industry.

[0006] The present invention accordingly provides novel chromophores.Preferably these chromophores exhibit 2^(o)-NLO properties. Optimallysuch chromophores can be employed in optical switches (particularly asdescribed in U.S. Ser. No. 09/357,201, and PCT/US00/19921, incorporatedby reference) that can perform several critical tasks for thetelecommunications industry—e.g., wavelength division multiplexing,wavelength division demultiplexing, performance as an add/drop filterand/or interconnect device. These and other objects and advantages ofthe present invention, as well as additional inventive features, will beapparent from the following description of the invention providedherein.

BRIEF SUMMARY OF THE INVENTION

[0007] The present invention provides novel substituted polyarylchromophoric compounds which desirably comprise a single diazo group,and optimally include a plurality of diazo groups.

[0008] One aspect of the present invention pertains to novelsubstituted-polyaryl diazo-compounds of the following formula (I):

[0009] wherein Ar₁ is selected from the group consisting of:

[0010] Ar² is selected from the group consisting of:

[0011] and if m=0; R¹ is an electron donating group selected from thegroup consisting of hydrogen, hydroxy, C₂₋₁₂alkoxy (optionallysubstituted with hydroxyl or amino), C₇₋₁₂dialkylamino (optionallysubstituted with hydroxyl or amino), and C₁₋₁₂alkylarylamino,(optionally substituted with hydroxyl or amino); R² is hydrogen,C₁₋₁₂alkyl, carboxy, hydroxy, C₁₋₁₂alkoxy, or halo; and at least one ofthe groups R³, R⁴ and R⁵ is an electron withdrawing group selected fromthe group consisting of hydrogen; cyano, COR², C₁₋₁₂mono- orpolyhaloalkyl, C₁₋₁₂alkenyl (substituted with an additional electronwithdrawing group), halo, nitro, sulfonyl, C₁₋₁₂alkylsulfonyl(optionally substituted), and arylsulfonyl (optionally substituted);while the other of the groups R³, R⁴ and R⁵ are, independently,C₁₋₁₂alkyl, hydroxy, C₁₋₁₂alkoxy, amino, C₁₋₁₂alkylarylamino (optionallysubstituted with hydroxyl or amino), diarylamino, (optionallysubstituted with hydroxyl or amino), hydrogen, cyano, COR², C₁₋₁₂mono-or polyhaloalkyl, C₁₋₁₂alkenyl (substituted with an additional electronwithdrawing group), halo, nitro, sulfonyl, C₁₋₁₂alkylsulfonyl(optionally substituted), or arylsulfonyl (optionally substituted); and

[0012] if m=1; R¹ is an electron donating group selected from the groupconsisting of hydrogen, hydroxy, amino, and C₁₋₁₂alkoxy (optionallysubstituted with hydroxyl or amino), C₁₋₁₂dialkylamino (substituted withhydroxyl or amino), C₁₋₁₂alkylarylamino (optionally substituted withhydroxyl or amino), and diarylamino (optionally substituted withhydroxyl or amino); R² is hydrogen, C₁₋₁₂alkyl, carboxy, hydroxy,C₁₋₁₂alkoxy, or halo; and at least one of the groups R³, R⁴ and R⁵ is anelectron withdrawing group selected from the group consisting ofhydrogen, cyano, COR², C₁₋₁₂mono- or polyhaloalkyl, C₁₋₁₂alkenyl(substituted with an additional electron withdrawing group), halo,nitro, sulfonyl, C₁₋₁₂alkylsulfonyl (optionally substituted) andarylsulfonyl (optionally substituted); while the other of the groups R³,R⁴ and R⁵ are, independently, C₁₋₁₂alkyl, hydroxy C₁₋₁₂alkoxy, amino,C₁₋₁₂alkylarylamino (optionally substituted with hydroxyl or amino),diarylamino (optionally substituted with hydroxyl or amino), hydrogen,cyano, COR², C₁₋₁₂mono- or polyhaloalkyl, C₁₋₁₂alkenyl (substituted withan additional electron withdrawing group), halo, nitro, sulfonylC₁₋₁₂alkylsulfonyl (optionally substituted), or arylsulfonyl (optionallysubstituted); and

[0013] if m=2-9; R¹ is an electron donating group selected from thegroup consisting of hydrogen, hydroxy, amino, C₁₋₁₂alkoxy (optionallysubstituted with hydroxyl or amino), C₁₋₁₂dialkylamino (optionallysubstituted with hydroxyl or amino), C₁₋₁₂alkylarylamino (optionallysubstituted with hydroxyl or amino), and diarylamino (optionallysubstituted with hydroxyl or amino); R² is hydrogen, C₁₋₁₂alkyl,carboxy, hydroxy, C₁₋₁₂alkoxy, or halo; and at least one of the groupsR³, R⁴ and R⁵ is an electron withdrawing group selected from the groupconsisting of hydrogen, cyano, COR², C₁₋₁₂mono- or polyhaloalkyl,C₁₋₁₂alkenyl (substituted with an additional electron withdrawinggroup), halo, nitro, sulfonyl, C₁₋₁₂alkylsulfonyl (optionallysubstituted), and arylsulfonyl (optionally substituted); while the otherof the groups R³, R⁴ and R⁵ are, independently, C₁₋₁₂alkyl, hydroxy,C₁₋₁₂alkoxy, amino, C₁₋₁₂alkylarylamino (optionally substituted withhydroxyl or amino), diarylamino (optionally substituted with hydroxyl oramino), hydrogen, cyano, COR², C₁₋₁₂mono- or polyhaloalkyl, C₁₋₁₂alkenyl(substituted with an additional electron withdrawing group), halo,nitro, sulfonyl, C₁₋₁₂alkylsulfonyl (optionally substituted), orarylsulfonyl (optionally substituted).

[0014] The polyaryl compounds can comprise a single diazo functionality,and optimally comprises a plurality of diazo linkages (i.e., at leasttwo linkages), and the compounds desirably comprise optical nonlinearsecond-order properties. Apart from being previously undescribed, thecompounds of the invention furthermore are novel in that they absorbmore in the UV or IR region than previously reported chromophoriccompounds.

[0015] In another aspect, the subject invention relates to compoundswhich desirably exhibit 2^(o)-NLO properties. The optical nonlinearsecond order compounds of the present invention also have unique lightabsorption maximum.

[0016] Another aspect of the invention is directed toward a compositioncontaining said compounds in combination with optically acceptablepolymer support.

[0017] Another aspect of this invention relates to compounds accordingto this invention that can be employed in devices such as amultifunctional optical switch. Other uses of the compounds of theinvention would be apparent to one skilled in the art.

[0018] Additional features and variations of the invention will beapparent to those skilled in the art from the entirety of thisapplication, including the detailed description, and all such featuresare intended as aspects of the invention. Likewise, features of theinvention described herein can be recombined into additional embodimentsthat also are intended as aspects of the inventions irrespective ofwhether the combination of features is specifically mentioned above (orherein) as an aspect or embodiment of the invention (e.g., any one ormore of the above aspects of the invention can be combined to produce avariety of substituted polyaryl chromophoric compounds with any desiredproperties). Also, only such limitations which are described herein ascritical to the invention should be viewed as such; variations of theinvention lacking limitations which have not been described herein ascritical are intended as aspects of the invention. In addition to theforegoing, the invention includes, as an additional aspect, allembodiments of the invention narrower in scope in any way than thevariations specifically mentioned above (and herein).

[0019] The detailed description and examples which follow are providedto enhance the understanding of the invention, but are not intended tolimit the scope of the invention.

DETAILED DESCRIPTION OF THE INVENTION

[0020] The invention provides for novel substituted-polyarylchromophoric compounds which desirably comprise a single diazo group,and optimally include a plurality of diazo groups.

[0021] As used herein, certain standard terms and phrases are employedin describing the invention. Some of the more commonly used terms andphrases have meanings, definitions, and explanations known in the artand are described in more detail below. Should there be any term that isleft undefined, or any possible ambiguity in the meaning of a term, thebroadest possible definition known in the optics/chemical fields that isconsistent with the scope and goals of the invention is to be applied.Also, like numbering is used for the same compounds in the Scheme and inthe descriptive text.

[0022] “Alkyl” refers to a cyclic, branched, or straight chain aliphaticgroup containing only carbon and hydrogen, for example, methyl, pentyl,and adamantyl. Alkyl groups can be unsubstituted or substituted with oneor more substituents, e.g., halogen, alkoxy, acyloxy, amino, hydroxyl,mercapto, carboxy, benzyloxy, aryl, and benzyl. Alkyl groups can besaturated or unsaturated (e.g., containing alkenyl or alkynyl subunitsat one or several positions). Typically, alkyl groups contain 1 to about12 carbon atoms, preferrably 1 to about 10, or 1 to about 8 carbonatoms.

[0023] “Aryl” refers to a monovalent aromatic carbocyclic orheterocyclic group having a single ring (e.g., phenyl), multiple rings(e.g., biphenyl), or multiple condensed rings (e.g., naphthyl oranthryl). Aryl groups can be unsubstituted or substituted with amino,hydroxyl, alkyl, heteroalkyl, alkoxy, halo, mercapto, sulfonyl, nitro,and other substituents. Typically, the aryl group is a substitutedsingle ring compound. For example, the aryl group is a substitutedphenyl ring.

[0024] The term “halo” or “halogen” is defined herein to includefluorine, bromine, chlorine, and iodine.

[0025] The term “alkoxy” is defined as —OR, wherein R is alkyl of one totwelve carbons attached to an oxygen forming such groups as methoxy,ethyloxy, butyloxy, and the like, and isomeric forms thereof

[0026] The term “hydroxy” is defined as —OH.

[0027] The term “amino” is defined as —NR₂, wherein each R,independently, is alkyl or hydrogen.

[0028] The term “cyano” is defined as —CN.

[0029] The term “sulfonyl” is defined as HOSO₂—

[0030] The term “alkylsulfonyl” is defined as R—SO₂—, where R is alkyl.

[0031] The term “arylsulfonyl ” is defined as R—SO₂—, where R is aryl.

[0032] The term “diazo” is defined as —N═N—.

[0033] The term “electron donating group” is defined as a group thattends to donate the electrons in a covalent bond away from itself Unlessotherwise specified, any appropriate electron donating group can beemployed according to the invention. Similarly, “optionally substituted”indicates that any appropriate group can be employed for substitution.

[0034] The term “electron withdrawing group” is defined as a group thattends to attract or draw the electrons in a covalent bond toward itself.Unless otherwise specified, any appropriate electron withdrawing groupcan be employed according to the invention.

[0035] The chemical formulas representing various compounds or molecularfragments in the specification and claims may contain variablesubstituents in addition to expressly defined structural features. Thesevariable substituents are identified by a letter or a letter followed bya numerical superscript, for example, “Ar^(in) or ”R^(in) where “i” isan integer. These variable substituents are either monovalent orbivalent, that is, they, represent a group attached to the formula byone or two chemical bonds. Groups R^(i) and R^(j) represent monovalentvariable substituents if attached to the formulaCH₃—CH₂—C(R^(i))(R^(j))H. When chemical formulas are drawn in a linearfashion, such as those above, variable substituents contained inparenthesis are bonded to the atom immediately to the left of thevariable substituent enclosed in parenthesis. When two or moreconsecutive variable substituents are enclosed in parenthesis, each ofthe consecutive variable substituents is bonded to the immediatelypreceding atom to the left which is not enclosed in parentheses. Thus,in the formula above, both R^(i) and R^(j) are bonded to the precedingcarbon atom.

[0036] Chemical formulas or portions thereof drawn in a linear fashionrepresents atoms in a linear chain. The symbol “—” in general representsa bond between two atoms in the chain. Thus, “HO—CH₂—CH(R^(j))—CH₃”represents a 2-substituted-1-hydroxypropane compound. In a similarfashion, the symbol “═” represents a double bond, e.g.,NH₂═N(R^(j))—CH₃.

[0037] The carbon atom content of variable substituents is indicated inone or two ways. The first method uses a prefix to the entire name ofthe variable such as “C₁-C₄”, where both “1” and “4” are integersrepresenting the minimum and maximum number of carbon atoms in thevariable. The prefix is separated from the variable by a space. Forexample, “C₁-C₄ alkyl” represents alkyl of 1 through 4 carbon atoms,(including isomeric forms thereof unless an express indication to thecontrary is given). Whenever this single prefix is given, the prefixindicates the entire carbon atom content of the variable being defined.Thus C₂-C₄ alkoxy describes a group CH₃—(CH₂)_(n)—O where n is zero, oneor two. By the second method, the carbon atom content of only eachportion of the definition is indicated separately by enclosing the“C_(i)-C_(j)” designation in parentheses and placing it immediately (nointervening space) before the portion of the definition being defined.By this optional convention (C₁-C₃) alkoxycarbonyl has the same meaningas C₂-C₄ alkoxycarbonyl because the “C₁-C₃” refers only to the carbonatom content of the alkoxy group. Similarly while both C₂-C₆ alkoxyalkyland (C₁-C₃) alkoxy-(C₁-C₃) alkyl define alkoxyalkyl groups containingfrom 2 to 6 carbon atoms, the two definitions differ since the formerdefinition allows either the alkoxy or alkyl portion alone to contain 4or 5 carbon atoms while the latter definition limits either of thesegroups to 3 carbon atoms. With respect to the above definition, C₁₋₇alkyl is methyl, ethyl, propyl, butyl, pentyl, hexyl, and the like, andisomeric forms thereof.

[0038] The invention pertains to novel substituted-polyaryl diazocompounds which exhibit 2^(o)-NLO properties as described herein andthat among other things, desirably can be utilized in a waveguide ormultifunctional optical switch. Formula (I) depicts the chemicalstructure of a diazo compound according to the present invention:

[0039] wherein Ar¹ is selected from the group consisting of:

[0040] Ar² is selected from the group consisting of:

[0041] and if m=0; R¹ is an electron donating group selected from thegroup consisting of hydrogen, hydroxy, C₂₋₁₂alkoxy (optionallysubstituted with hydroxyl or amino), C₇₋₁₂dialkylamino (optionallysubstituted with hydroxyl or amino), and C₁₋₁₂alkylarylamino,(optionally substituted with hydroxyl or amino); R² is hydrogen,C₁₋₁₂alkyl, carboxy, hydroxy, C₁₋₁₂alkoxy, or halo; and at least one ofthe groups R³, R⁴ and R⁵ is an electron withdrawing group selected fromthe group consisting of hydrogen, cyano, COR², C₁₋₁₂mono- orpolyhaloalkyl, C₁₋₁₂alkenyl (substituted with an additional electronwithdrawing group), halo, nitro, sulfonyl, C₁₋₁₂alkylsulfonyl(optionally substituted), and arylsulfonyl (optionally substituted);while the other of the groups R³, R⁴ and R⁵ are, independently,C₁₋₁₂alkyl, hydroxy, C₁₋₁₂alkoxy, amino, C₁₋₁₂alkylarylamino (optionallysubstituted with hydroxyl or amino), diarylamino, (optionallysubstituted with hydroxyl or amino), hydrogen, cyano, COR², C₁₋₁₂mono-or polyhaloalkyl, C₁₋₁₂alkenyl (substituted with an additional electronwithdrawing group), halo, nitro, sulfonyl, C₁₋₁₂alkylsulfonyl(optionally substituted), or arylsulfonyl (optionally substituted); and

[0042] if m=1; R¹ is an electron donating group selected from the groupconsisting of hydrogen, hydroxy, amino, and C₁₋₁₂alkoxy (optionallysubstituted with hydroxyl or amino), C₁₋₁₂dialkylamino (substituted withhydroxyl or amino), C₁₋₁₂alkylarylamino (optionally substituted withhydroxyl or amino), and diarylamino (optionally substituted withhydroxyl or amino); R² is hydrogen, C₁₋₁₂alkyl, carboxy, hydroxy,C₁₋₁₂alkoxy, or halo; and at least one of the groups R³, R⁴ and R⁵ is anelectron withdrawing group selected from the group consisting ofhydrogen, cyano, COR², C₁₋₁₂mono- or polyhaloalkyl, C₁₋₁₂alkenyl(substituted with an additional electron withdrawing group), halo,nitro, sulfonyl, C₁₋₁₂alkylsulfonyl (optionally substituted) andarylsulfonyl (optionally substituted); while the other of the groups R³,R⁴ and R⁵ are, independently, C₁₋₁₂alkyl, hydroxy, C₁₋₁₂alkoxy, amino,C₁₋₁₂alkylarylamino (optionally substituted with hydroxyl or amino),diarylamino (optionally substituted with hydroxyl or amino), hydrogen,cyano, COR², C₁₋₁₂mono- or polyhaloalkyl, C₁₋₁₂alkenyl (substituted withan additional electron withdrawing group), halo, nitro, sulfonyl,C₁₋₁₂alkylsulfonyl (optionally substituted), or arylsulfonyl (optionallysubstituted); and.

[0043] if m=2-9; R¹ is an electron donating group selected from thegroup consisting of hydrogen, hydroxy, amino, C₁₋₁₂alkoxy (optionallysubstituted with hydroxyl or amino), C₁₋₁₂dialkylamino (optionallysubstituted with hydroxyl or amino), C₁₋₁₂alkylarylamino (optionallysubstituted with hydroxyl or amino), and diarylamino (optionallysubstituted with hydroxyl or amino); R² is hydrogen, C₁₋₁₂alkyl1,carboxy, hydroxy, C₁₋₁₂alkoxy, or halo; and at least one of the groupsR³, R⁴ and R⁵ is an electron withdrawing group selected from the groupconsisting of hydrogen, cyano, COR², C₁₋₁₂mono- or polyhaloalkyl,C₁₋₁₂alkenyl (substituted with an additional electron withdrawinggroup), halo, nitro, sulfonyl, C₁₋₁₂alkylsulfonyl (optionallysubstituted), and arylsulfonyl (optionally substituted); while the otherof the groups R³, R⁴ and R⁵ are, independently, C₁₋₁₂alkyl, hydroxy,C₁₋₁₂alkoxy, amino, C₁₋₁₂alkylarylamino (optionally substituted withhydroxyl or amino), diarylamino (optionally substituted with hydroxyl oramino), hydrogen, cyano, COR²C₁₋₁₂mono- or polyhaloalkyl, C₁₋₁₂alkenyl(substituted with an additional electron withdrawing group), halo,nitro, sulfonyl, C₁₋₁₂alkylsulfonyl (optionally substituted), orarylsulfonyl (optionally substituted).

[0044] The chromophoric compounds of this invention are prepared asdescribed briefly here and in more detail in the examples which follow.Scheme 1 illustrates the general method and specific examples ofsynthesizing the chromophoric compounds of the invention, as furtherdescribed in the Examples which follow.

[0045] Preferably, chromophores are synthesized using as a startingpoint an appropriately substituted aniline, preferably containing aelectron withdrawing group (EWG) at the 4-position (R¹), such as acyano, carbonyl, C₁₋₁₂mono- or polyhaloalkyl, C₁₋₁₂alkenyl, substitutedwith an additional electron withdrawing group; halo, nitro, sulfonylC₁₋₁₂alkylsulfonyl or arylsulfonyl derivative. These materials arereadily available from a number of commercial vendors or alternatively,are known in the chemical literature and may be readily prepared by oneskilled in the art. These aniline compounds are then subsequentlyreacted following procedures known, or readily acquired by one skilledin the art. In one embodiment, the appropriately substituted aniline isfirst treated with an acid catalyst and a diazotizing reagent, such assodium nitrite (Y═Na) or nitrosyl sulfuric acid (Y═HSO₃), and thensubsequently treated with an sufficiently electron rich,substituted-benzene such that the subsequent aromatic substitutionreaction provides, in a one-pot reaction sequence, the respective crudediazo-linked, substituted diary compounds (Compounds 1-3,5) in moderateto high yields (i.e., Scheme 1, reaction depicted proceeding right). Theproducts (Compounds 1-3,5) may then be further purified followingchromatographic techniques well known in the art. Examples of acidcatalysts that can be used include hydrochloric acid, phosphoric acid,and sulfuric acid. Examples of electron rich, substituents on benzeneinclude, but are not limited to, C₁₋₁₂alkyl, hydroxyl, C₁₋₁₂alkoxy,amino, C₁₋₁₂dialkylamino, and the like, and combinations thereof.

[0046] In another embodiment, the substituted-polyaryl compounds of theinvention have multiple diazo linking groups between the substitutedaryl groups. In these cases the extended diazo-linkage is formed priorto the substitution reaction with the final electron rich,substituted-benzene. This is also shown in Scheme 1 (i.e., reactiondepicted proceeding downward). For example, the starting aniline istreated with an acid catalyst and diazotizing reagent, such as sodiumnitrite or nitrosyl sulfuric acid, as in the method above, and thensubsequently treated with another, substituted-aniline such that thesubsequent aromatic substitution reaction provides a diazo-linkedarylaniline intermediate (Compounds 3 and 5). This process can berepeated multiple times to form polydiazo aryl aniline intermediatesbefore terminating the reaction sequence by reaction with the finalelectron rich, substituted-benzene (Compounds 4 and 6).

[0047] A third embodiment to produce the substituted-polyaryl compoundsof the invention involves a similar set of reactions as that disclosedin Scheme 1 with either a substituted 2-amino-benzothiazole or asubstituted 2-amino-thiazole instead of the starting substitutedaniline. Examples of some substituted-polyaryl-diazo chromophoriccompounds of the present invention are given in Table 1 and Table 2.TABLE 1 Phenyl diazo chromophores

Compound # m R¹ R² R^(2′) R^(2″) R^(′″) R³ R⁴ R⁵ 1 0 OH H H — — SO₂CH₃ HH 2 0 OH CH₃ H — — SO₂CH₃ H H 3 0 NH₂ CH₃ H — — SO₂CH₃ H H 4 1 OH H HCH₃ H SO₂CH₃ H H 5 0 NH₂ OCH₃ OCH₃ — — NO₂ H H 6 1 N(C₂H₅)(C₂H₅OH) H HOCH₃ OCH₃ NO₂ H H 7 0 NH₂ H H H H CF₃ H H 8 0 N(C₂H₅)(C₂H₅OH) H H H HCF₃ H NO₂ 9 0 NH₂ H H CH₃ H CF₃ H NO₂ 10 0 N(C₂H₅)(C₂H₅OH) H H H H NO₂CF₃ H 11 0 NH₂ H H CH₃ H NO₂ CF₃ H 12 0 NH₂ H H CH₃ H NO₂ H NO₂ 13 1OC₈H₁₇ H H CH₃ H SO₂CH₃ H H 14 1 N(C₂H₅)₂ H H CH₃ H SO₂CH₃ H H 15 1 OHCH₃ H CH₃ H SO₂CH₃ H H 16 1 OH H H CH₃ H NO₂ H H 17 1 OH CH₃ H CH₃ H NO₂H H 18 1 O(CH₂)₇OH H H CH₃ H CF₃ H H 19 1 N(C₂H₅)(C₂H₅OH) H H OCH₃ OCH₃NO₂ H H 20 1 NH₂ CH₃ H H H NO₂ H H 21 1 O(CH₂)₇OH H H CH₃ H SO₂CH₃ H H22 1 OH H H CH₃ H CF₃ H H 23 1 OH H H CH₃ H F H H 24 1 N(C₂H₅)(C₂H₅OH) HH CH₃ H CF₃ H NO₂ 25 1 N(C₂H₅)(C₂H₅OH) H H CH₃ H NO₂ CF₃ H 26 1N(C₂H₅)(C₂H₅OH) H H CH₃ H NO₂ H NO₂ 27 1 NH₂ CH₃ H CH₃ H NO₂ H NO₂ 28 1OH H H H CO₂H SO₂CH₃ H H 29 1 OH H H CH₃ H SO₂CH₃ H H 30 1 NH₂ CH₃ H CH₃H SO₂CH₃ H H 31 2 N(C₂H₅)₂ H H CH₃ H SO₂CH₃ H H 32 2 N(C₂H₅)(C₂H₅OH) H HCH₃ H SO₂CH₃ H H 33 2 OH H H CH₃ H SO₂CH₃ H H 34 2 O(CH₂)₇OH H H CH₃ HSO₂CH₃ H H 35 2 O(CH₂)₇OH H H H H OCH₃ H H 36 2 NH₂ CH₃ H CH₃ H SO₂CH₃ HH 37 2 OH H H CH₃ H NO₂ H H 38 2 OC₈H₁₇ H H CH₃ H NO₂ H H 39 2NCH₃(C₈H₁₇) H H CH₃ H NO₂ H H 40 2 NH₂ H H CH₃ H NO₂ H H 41 2N(C₂H₅)(C₂H₅OH) H H CH₃ H NO₂ H NO₂ 42 3 N(C₂H₅)₂ H H CH₃ H SO₂CH₃ H H43 3 OH H H CH₃ H SO₂CH₃ H H 44 3 NCH₃(C₈H₁₇) H H CH₃ H NO₂ H H

[0048] TABLE 2 Heteroaryl diazo chromophores

Compound # m Ar¹ Ar² Ar³ 45 0

46 0

47 0

48 0

49 1

50 1

51 1

52 1

53 1

54 1

55 1

[0049] The substituted-polyaryl diazo chromophoric compounds of theinvention preferably comprise second-order nonlinear optical (2^(o)-NLO)properties as set forth herein, and further described below. Asecond-order nonlinear optical (2^(o)-NLO) compound is a compound thatis “optically active”—i.e., its index of refraction changes due to anapplied electric field, and the change is proportional to the square ofthe applied electric field. The electric field is generated with anyappropriate power source (e.g., AC or DC power source), and communicatedto a chromophore (e.g., present in a polymer contained in an opticalwaveguide or switch) by means of an electrode. Any electrode having theability to conduct charge and capable of functioning as an “electrode”as that term is understood in the art can be employed. Generally, anelectrode need only supply a small amount of voltage, e.g., from 0 toabout 50 volts, although in certain applications, it may be preferableto employ a higher voltage.

[0050] Desirably, for use in an optical waveguide or switch, achromophore according to the invention has an absorption wavelength frombetween about 200 nm and about 800 nm, preferably from between about 300nm and about 600 nm. The preferred chromophores according to theinvention also desirably have an effective cis-trans isomerizationprocess when excited at their absorption wavelengths. Also, desirably,the chromophores are such that polarization alone can be used to inducealignment in the chromophores (e.g., as described in Rochon et al.,“Optically Induced and Erased Birefringence and Dichroism in AzoaromaticPolymers”, Appl. Phys. Lett. 60, pages 4-5 (1992); Kim et al., “LaserInduced Holographic Surface Relief gratings on Nonlinear Optical PolymerFilms”, Appl. Phys. Lett. 66, pages 1166-1168, (1995)) which is helpfulin preparing optical waveguides or switches. Optimally this inducedalignment will be in the direction to reduce interaction with theincident polarized light. These materials according to the inventionthus provide great flexibility in terms of chemical modification, suchmodification which may be desirable in optimizing the properties of thecompound for use in optical applications (although uses for thechromophores other than in optic switches and waveguides arecontemplated according to the invention). For instance, from a dialkylamino nitro diazo compound it is possible to change the electron donorin the chromophore from nitrogen to oxygen and the electron acceptorfrom nitro to sulfone to get an alkoxy sulfone diazo compound.

[0051] According to the invention, and, as further described below, anoptical switch or waveguide can be obtained that utilizes the compoundsdisclosed herein with 2^(o)-NLO properties. In particular, compoundsdisclosed herein can be utilized in an optical switch or waveguide asdescribed in U.S. Ser. No. 09/357,201 and PCT/US00/19921, incorporatedby reference in their entireties. A “waveguide” is an entity of materialboundaries or structures for guiding electromagnetic waves or energy(i.e., carrying one or more optical signals). An “optical switch” is adevice that is capable of changing the path of light from one waveguideto another (e.g., an optical wavelength divisionmultiplexer/demultiplexer, optical add/drop multiplexer, and/or opticalinterconnect). A “device” includes a single entity such as a waveguideor any combination of elements (e.g., optical switch such as opticalwavelength division multiplexer/demultiplexer, optical add/dropmultiplexer, optical interconnect, and the like) either alone, or, in ahigher level of organization (e.g., present in a system or subsystemsuch as a board or motherboard). The compounds with 2^(o)-NLO propertiesthat are utilized in these devices are typically obtained by chemicalconjugation of a 2^(o)-NLO chromophore onto a polymer or by merelymixing a 2^(o)-NLO chromophore with a polymer in a process commonlyknown as “doping” (e.g., as described in Marder et al., supra, Saaedehet al., supra, Yu et al., supra, U.S. Ser. No. 09/357,201,PCT/US00/19921, and references cited therein, as well as in otherreferences). This renders it possible to induce and manipulate therefractive index of the polymer films by using the appropriatewavelength of light. The chromophore incorporated in the polyimide canbe any chromophore, but desirably is a chromophore including, but notlimited to: (a) the novel chromophores described herein, or (b) thosechromophores depicted in Table 3 (which are known and have beendescribed in the art). In Table 3 below, “μ” is the dipolar moment ofthe molecule, “β” is the hyperpolarizability, and “λ” is the wavelengthTABLE 3

m R¹ R³ μβ × 10⁴⁸ (esu) λmax (nm) 0 N(CH₃)₂ NO₂ 751 480 0 N(CH₃)₂ NO₂788 486 0 N(Ph)₂ NO₂ 996 494 0 N(C₂H₅)₂ CHC(CN)₂ 1,360 526 0 N(Ph)₂C₂(CN)₃ 2,776 602 1 N(4-NH₂Ph)₂ NO₂ 19,000 504 1 N(C₂H₅)₂ C₂(CN)₃ 24,000—

[0052] The concentration of chromophores in a polymer can be carefullyadjusted by copolymerization to control the refractive index at theexpense of the nonlinearity (e.g., as described in Girton et al.,“Electrooptic Polymer Mach-Zehnder Modulator”, In ACS Symposium Series601, Polymers for Second-Order Nonlinear Optics (Washington D.C. 1995)456-468, and Keil, “Realization of IO-Polymer-Components and presentstate in Polymer Technology”, In, Intergrated Optics and Micro-Opticswith Polymers (Stuttgart-Leipzeig: B. G. Teubner Verlagsgesellscaft,1993), 273). In “doping” techniques it is preferable that theconcentration of the chromophore be between about 3% and about 10% ofthe total polymer mixture. By changing the pendant chromophore in thepolymer employed, devices having unique and highly differentiableoptical properties can be obtained. Other variations such as would beobvious to one skilled in the art are contemplated by the invention.Thus, the present invention optimally provides for a uniquely designedfamily of substituted-polyaryl diazo chromophoric compounds, which canbe optionally combined with polymers to be used in devices, such as aoptical switch.

[0053] The invention will now be described with reference to thefollowing illustrative Examples. The following Examples are by means ofillustration, not limitation. Of course, variation of these Examples inthe spirit and scope of the invention are contemplated herein.

EXAMPLE 1 Preparation of1-[(4-hydroxyphenyl)diazenyl]-4-(methylsulfonyl)benzene (Compound 1)

[0054] As described herein, the structure ofl-[(4-hydroxyphenyl)diazenyl]-4(methylsulfonyl)benzene (Compound 1) is:

[0055] In this Example and all subsequent Examples, reagents werepurchased from Aldrich, Acros, or Sigma and used without furtherpurification. However, comparable materials from other vendors can beemployed instead. All temperatures are in degrees Centrigrade. Whensolvent pairs are used, the ratios of solvents used are volume/volume(v/v). When the solubility of a solid in a solvent is used, the ratio ofthe solid to the solvent is weight/volume (wt/v). Reactions withmoisture-sensitive reagents were performed under nitrogen atmosphere.Determination of the concentration of solutions after workup wasperformed by reduced pressure rotary evaporation. Preparative thin-layerchromatography (TLC) were performed using EM silica gel (SG) 60 F254plates (20×20 cm, thickness 2 mm). NMR refers to nuclear magneticresonance spectroscopy; ¹H NMR refers to proton nuclear magneticresonance spectroscopy with chemical shifts reported in ppm downfieldfrom tetramethylsilane. Mass-spectra (MS) refers to mass spectrometryexpressed as m/e or mass/charge unit and was obtained using electronimpact (EI) technique. [M+H]⁺ refers to the positive ion of a parentplus a hydrogen atom. IR refers to infrared spectroscopy; FTIR refers toFourier Transform IR.

[0056] For these studies, p-Methylsulfonylaniline (Ulman, A. et. al.,JACS, 112, 7083,(1990)) (0.96 g, 5.61 mmol) was sequentially treatedwith hydrogen chloride (HCl) (10 ml of a 6M solution, 6 mmol) and sodiumnitrite (0.426 g, 6.18 mmol) while the temperature was maintainedbetween 0-5° C. The reagents were allowed to dissolve and the resultingsolution was allowed to stir for about 15 minutes. The resultingdiazonium compound was then treated with hydrogen tetrafluoroborate togive a tetrafluoroborate diazonium salt. The resulting tetrafluoroborate(BF₄) diazonium salt was divided into two portions. Half of thediazonium salt was added to a solution of phenol (0.22 g, 2.3 mmol) andpotassium hydroxide (KOH) (0.11 g, 2 mmol) in tetrahydrofuran (THF). Theresulting orange-red mixture was stirred for 0.5 h and then neutralizedwith acetic acid (HOAc) to give a yellow-orange solid. This solid wasfiltered and recrystallized from THF/Hexanes to give 0.4 g (63%) ofCompound 1.

EXAMPLE 2 Preparation of1-[(4-hydroxy-2-methylphenyl)diazenyl]-4-(methylsulfonyl)benzene(Compound 2)

[0057] As described herein, the structure of1-[(4-hydroxy-2-methylphenyl)diazenyl]-4-(methylsulfonyl)benzene(Compound 2) is:

[0058] For these studies, half of the diazonium salt from example 1 wasadded to a solution of m-cresol (0.285 g, 2.34 mmol) and KOH (0.13 g, 2mmol) in THF. The resulting red mixture was stirred for 0.5 h and thenneutralized with HOAc to give a orange solid. This solid was filteredand recrystallized from THF/Hexanes to give 0.35 g (58%) of Compound 2.

EXAMPLE 3 Preparation of 1-[(4-amino-2-methylphenyl)diazenyl]-4-(methylsulfonyl)benzene (Compound 3)

[0059] As described herein, the structure of1-[(4-amino-2-methylphenyl)diazenyl]-4-(methylsulfonyl)benzene (Compound3) is:

[0060] For their studies, p-Methylsulfonylaniline (1.42 g, 8.3 mmol) wassequentially treated with HCl (15 ml of a 6M solution, 9 mmol) andsodium nitrite (0.66 g, 9.12 mmol) while the temperature was maintainedbetween 0-5° C. The reagents were allowed to dissolve and the resultingsolution was allowed to stir for an about 15 minutes. The resultingdiazonium compound was then treated with m-toluidine (0.9 g, 8.4 mmol)in THF, and allowed to stir for about 15 minutes to 1 h. To theresulting red-orange mixture was added sodium acetate NaOAc) (2 g, 2mmol) or water and allowed to stir for about 16 h. The precipitatedorange solid was filtered, sequentially washed with water/ethanol andhexanes, and dried under vacuum and recrystallized from EtOAc/Hexane togive 1.96 g (73.3%) of Compound 3.

EXAMPLE 4 Preparation of1-({4-[(4-hydroxyphenyl)diazenyl]-2-methylphenyl}diazenyl)-4-(methylsulfonyl)-benzene(Compound 4)

[0061] As described herein, the structure of 1-({4[(4-hydroxyphenyl)diazenyl]-2-methylphenyl}diazenyl)-4-(methylsulfonyl)-benzene (Compound4) is:

[0062] Compound 3 (0.85 g, 2:94 mmol) was sequentially treated with aHCl/phosphoric (H₂PO₄)/sulfuric acid (H₂SO₄) mixture and nitrosylsuilfric acid (5 ml) while the temperature was maintained at about −15°C. The reagents were allowed to dissolve and the resulting solution wasallowed to stir for an about 15 minutes. The resulting diazonium mixturewas then treated with urea (0.5 g), stirred for about 10 minutes;treated with hydrogen tetrafluoroborate (15 ml), and stirred for anadditional 20 minutes to give the tetrafluoroborate diazonium salt. Theresulting tetrafluoroborate (BF₄) diazonium salt was filtered then addedto a solution of phenol (0.31 g, 3.2 mmol) and sodium hydroxide (NaOH)(0.15 g, 3 mmol1) or potassium hydroxide in THF/water (1:1). Theresulting pink mixture was stirred for 0.5 h and then neutralized with1N HCl to give a yellow-orange solid. This solid was filtered andrecrystallized from THF/Hexanes or EtOH/H₂O to give 0.92 g (79%) ofCompound 4.

EXAMPLE 5 Preparation of 1-({4-[(4-(7-hydroxy-n-heptoxyphenyl)diazenyl]-2-methylphenyl}diazenyl)-4-(methylsulfonyl)-benzene (Compound21)

[0063] As described herein, the structure of1-({4-[(4-(7-hydroxy-n-heptoxyphenyl)diazenyl]-2-methylphenyl}diazenyl)-4-(methylsulfonyl)-benzene (Compound21) is:

[0064] A mixture of compound 4(4.61 g, 11.7 mmol),6-bromo-1-hexanol(2.50 g, 14.0 mmol), and K₂CO₃ (7.00 g, 70.0 mmol) in 35 mL of dryacetone was refluxed for 48 h. The resulting orange-red mixture wastreated with H₂O to dissolve excess K₂CO₃ and then filtered, washedthoroughly with H₂O then dried. The solid was recrystallized fromCHCl₃/Hexane to give compound 21 (6.90 g, 89.0%).

EXAMPLE 6 Preparation of2[4-(1,3-dioxoisoindolin-2-yl)-2-(2-{4-[(3-methyl-4-{[4-(methylsulfonyl)phenyl]diazenyl}phenyl)diazenyl]phenoxy}ethoxyl)phenyl]isoindoline-1,3-dione(Compound 56)

[0065] As described herein, the structure of2-[4-(1,3-dioxoisoindolin-2-yl)-2-(7-{4-[(3-methyl-4-{[4-(methylsulfonyl)phenyl]diazenyl}phenyl)diazenyl]phenoxy}heptoxy)phenyl]isoindoline-1,3-dione(Compound 56) is:

[0066] To a solution of2-[4-(1,3-dioxoisoindolin-2-yl)-2-hydroxyphenyl]isoindoline-1,3-dioneprepared as described in Yu et al. Macromolecules 28: 784 (1995); 29:6139, (1996); and J. Am. Chem. Soc. 117: 11680 (1995) (1.82 g, 4.76mmol) 60 mL of anhydrous DMF under N₂, was added compound 21 (2.35 g,4.76 mmol) and triphenylphosphine (1.90 g, 7.30 mmol). The resultedsolution was treated dropwise with a solution of diethylazidocarboxylate(1.27 g, 7.3 mmol) in 5 mL of anhydrous DMF. The reaction mixture wasstirred for five hours, then precipitated into 100 mL of methanol. Theproduct was collected by filtration and chromatographed using CHCl₃/MeOH(99:1) to give compound 56 (1.90 g, 47%), ¹H NMR (CDCl₃) δ 8.1 (d, J=8.7Hz, 2H), 8.1 (d, J=8.7 Hz, 2H), 8.0 (d, 2H), 7.9 (s, 1H), 7.8 (m, 2H),7.0 (d, J=8.9 Hz, 2H), 4.1 (t, J=6.5 Hz, 2H), 3.7 (t, J=6.5 Hz, 2H), 3.4(t, J=6.4 Hz, 1H), 3.1 (s, 3H), 2.8 (s, 3H), 1.8 (m, 2H), 1.5 (m, 6H).Compound 56 was incorporated into a polymer backbone following theliterature procedure described in Saadeh et al., Macromolecules 30(18):5403 (1997). A ¹H NMR spectra was obtained.

EXAMPLE 7 Preparation of1-[(4amino-2.5-dimethoxyphenyl)diazenyl]-4-nitrobenzene (Compound 5)

[0067] As described herein, the structure of1-[(4-amino-2,5-dimethoxyphenyl) diazenyl]-4-nitrobenzene (Compound 5)is:

[0068] A diazonium salt synthesized from 4-nitroaniline using theprocedure of example 1 (1.4 g, 5.9 mmol) was added portionwise to asolution of2,4-dimethoxyaniline (0.97 g, 6.3 mmol) in dimethylformamideDMF) (20 ml). The resulting red mixture was stirred for 1.5 h, filtered,and the resulting solid recrystallized from ethyl acetate(EtOAc)/Hexanes to give 1.3 g (70.6%) of Compound 5.

EXAMPLE 8 Preparation of1-({4-[(4-(2-hydroxyethyl)ethylaminophenyl)diazenyl]-2.5-dimethoxyphenyl}diazenyl)-4-nitrobenzene(Compound 6)

[0069] As described herein, the structure of 1-({4-[(4-(2-hydroxyethyl)ethylaminophenyl)diazenyl]-2,5-dimethoxyphenyl}diazenyl)-4-nitrobenzene(Compound 6) is:

[0070] Compound 5 (0.4 g, 1.29 mmol) was sequentially treated dropwisewith a H₂PO₄/H₂SO₄ mixture (30 ml of a 4:1 mixture) and sodium nitrite(0.1 g 1.55 mmol) while the temperature was maintained at about 0° C.The reagents were allowed to dissolve and the resulting solution wasallowed to stir for about 20 minutes. The resulting diazonium mixturewas then treated with urea (0.5 g), stirred for about 10 minutes,treated with hydrogen tetrafluoroborate (15 ml), and stirred for anadditional 20 minutes to give the tetrafluoroborate diazonium salt. Theresulting tetrafluoroborate diazonium salt was filtered and added to asolution ofN,N-ethyl-2-hydroxyethylaniline in THF. The resulting violetmixture was neutralized with NaOAc (5.0 g), stirred for about 0.5 h, andconcentrated to give a green solid. This solid was filtered andrecrystallized from THF/Hexanes to give 0.37 g (59%) of Compound 6.

EXAMPLE 9 Preparation of1-({4-[(4-(2-hydroxyethyl)ethylaminophenyl)diazenyl]-2-methylphenyl}diazenyl)-2,4-dinitrobenzene(Compound 26)

[0071] As described herein, the structure of1-({4-[(4-(2-hydroxyethyl)ethylaminophenyl)diazenyl]-2-methylphenyl}diazenyl)-2,4-dinitrobenzene(Compound 26) is

[0072] A diazonium salt was prepared by dissolving 2,4dinitroaniline inan acid mixture of H₃PO₄/H₂SO₄ and then treating the mixture with sodiumnitrite while the temperature was maintained between 0-5° C. Thediazonium salt was isolated as its tetrafluoroborate salt following theprevious procedures. The diazonium salt (2.00 g, 7.0 mmol) was thenadded to a solution of m-toluidine (0.94 g, 8.80 mmol) in 20 mL THF. Theresulting red mixture was stirred for 1 h and a solid precipitated. Thesolid was filtered and recrystallized from THF/Hexane to give 1.50 g(71%) of compound 12. Compound 12 was again diazotized and separated asits tetrafluoroborate salt following the previous procedure. A solutionofN-ethyl-N—(B-hydroxyethyl)aniline(0.30 g,1.80 mmol) in 30 mL of aTHF/Acetone mixture(1:1), was treated with the diazonium salt(0.60 g,1.53 mmol). The resultant purple solution was stirred for a further 1hour then treated with water (20 mL). The precipitate was filtered andrecrystallized from acetone-hexane to give the pure chromophore 26 (0.40g, 45%). ¹H NMR (DMSO) δ 8.9 (s, 1H), 8.6 (d, J=8.7 Hz, 1H), 8.0 (d,J=8.7 Hz, 1H), 7.8 (m, 3H), 7.7 (m, 2H), 6.9 (d, J=8.6 Hz, 2H), 3.6 (m,2H), 3.5 (m, 4H), 3.3 (s, 1H), 2.8 (s, 3H), 2.5 (s, 3H), 1.2 (t, J=6.7Hz, 3H). Compound 26 was incorporated into a polymer backbone followingthe literature procedure described in Saadeh et al., Macromolecules30(18): 5403 (1997). A ¹H NMR spectra was obtained.

[0073] All the references cited herein are hereby incorporated in theirentireties by reference, as are, in particular, U.S. Ser. No. 09/357,201and PCT/US00/19921.

[0074] While the present invention has been described in terms ofspecific embodiments, it is understood that variations and modificationswill occur to those in the art, all of which are intended as aspects ofthe present invention. Accordingly, only such limitations as appear inthe claims should be placed on the invention Although the applicant(s)invented the full scope of the claims, the claims are not intended toencompass within their scope the prior art work of others. Therefore, inthe event that statutory prior art within the scope of a claim isbrought to the attention of the applicant(s) by a Patent Office or otherentity or individual, the applicant(s) reserve the right to exerciseamendment rights under applicable patent laws to redefine the subjectmatter of such a claim to specifically exclude such statutory prior artor obvious variations of prior art from the scope of such a claim.Variations of the invention defined by such amended claims also areintended as aspects of the invention. Accordingly, this inventionincludes all modifications encompassed within the spirit and scope ofthe invention.

What is claimed is:
 1. A compound of the formula:

wherein Ar¹ is selected from the group consisting of:

 Ar² is selected from the group consisting of:

 and if m=0; R¹ is an electron donating group selected from the groupconsisting of hydrogen, hydroxy, C₂₋₁₂alkoxy (optionally substitutedwith hydroxyl or amino), C₇₋₁₂dialkylamino (optionally substituted withhydroxyl or amino), and C₁₋₁₂alkylarylamino, (optionally substitutedwith hydroxyl or amino); R² is hydrogen, C₁₋₁₂alkyl, carboxy, hydroxy,C₁₋₁₂alkoxy, or halo; and at least one of the groups R³, R⁴ and R⁵ is anelectron withdrawing group selected from the group consisting ofhydrogen, cyano, COR², C₁₋₁₂mono- or polyhaloalkyl, C₁₋₁₂alkenyl(substituted with an additional electron withdrawing group), halo,nitro, sulfonyl, C₁₋₁₂alkylsulfonyl (optionally substituted), andarylsulfonyl (optionally substituted); while the other of the groups R³,R⁴ and R⁵ are, independently, C₁₋₁₂alkyl, hydroxy, C₁₋₁₂alkoxy, amino,C₁₋₁₂alkylarylamino (optionally substituted with hydroxyl or amino),diarylamino, (optionally substituted with hydroxyl or amino), hydrogen,cyano, COR², C₁₋₁₂mono- or polyhaloalkyl, C₁₋₁₂alkenyl (substituted withan additional electron withdrawing group), halo, nitro, sulfonyl,C₁₋₁₂alkylsulfonyl (optionally substituted), or arylsulfonyl (optionallysubstituted); and if m=1; R¹ is an electron donating group selected fromthe group consisting of hydrogen, hydroxy, amino, and C₁₋₁₂alkoxy(optionally substituted with hydroxyl or amino), C, ₁₋₁₂dialkylamino(substituted with hydroxyl or amino), C₁₋₁₂alkylarylamino (optionallysubstituted with hydroxyl or amino), and diarylamino (optionallysubstituted with hydroxyl or amino); R² is hydrogen, C₁₋₁₂alkyl,carboxy, hydroxy, C₁₋₁₂alkoxy, or halo; and at least one of the groupsR³, R⁴ and R⁵ is an electron withdrawing group selected from the groupconsisting of hydrogen, cyano, COR², C₁₋₁₂mono- or polyhaloalkyl,C₁₋₁₂alkenyl (substituted with an additional electron withdrawinggroup), halo, nitro, sulfonyl, C₁₋₁₂alkylsulfonyl (optionallysubstituted) and arylsulfonyl (optionally substituted); while the otherof the groups R³, R⁴ and R⁵ are, independently, C₁₋₁₂alkyl, hydroxy,C₁₋₁₂alkoxy, amino, C₁₋₁₂alkylarylamino (optionally substituted withhydroxyl or amino), diarylamino (optionally substituted with hydroxyl oramino), hydrogen, cyano, COR², C₁₋₁₂mono- or polyhaloalkyl, C₁₋₁₂alkenyl(substituted with an additional electron withdrawing group), halo,nitro, sulfonyl, C₁₋₁₂alkylsulfonyl (optionally substituted), orarylsulfonyl (optionally substituted); and if m=2-9; R¹ is an electrondonating group selected from the group consisting of hydrogen, hydroxy,amino, C₁₋₁₂alkoxy (optionally substituted with hydroxyl or amino),C₁₋₁₂dialkylamino (optionally substituted with hydroxyl or amino),C₁₋₁₂alkylarylamino (optionally substituted with hydroxyl or amino), anddiarylamino (optionally substituted with hydroxyl or amino); R2 ishydrogen, C₁₋₁₂alkyl, carboxy, hydroxy, C ₁₋₁₂alkoxyl, or halo; and atleast one of the groups R³, R⁴ and R⁵ is an electron withdrawing groupselected from the group consisting of hydrogen, cyano, COR², C₁₋₁₂mono-or polyhaloalkyl, C₁₋₁₂alkenyl (substituted with an additional electronwithdrawing group), halo, nitro, sulfonyl, C₁₋₁₂alkylsulfonyl(optionally substituted), and arylsulfonyl (optionally substituted);while the other of the groups R³, R⁴ and R⁵ are, independently,C₁₋₁₂alkyl, hydroxy, C₁₋₁₂alkoxy, amino, C₁₋₁₂alkylarylamino (optionallysubstituted with hydroxyl or amino), diarylamino (optionally substitutedwith hydroxyl or amino), hydrogen, cyano, COR², C₁₋₁₂mono- orpolyhaloalkyl, C₁₋₁₂alkenyl (substituted with an additional electronwithdrawing group), halo, nitro, sulfonyl, C₁₋₁₂alkylsulfonyl(optionally substituted), or arylsulfonyl (optionally substituted). 2.The compound in accordance with claim 1 wherein R² is hydrogen, methyl,or methoxy, R³, R⁴ and R⁵ are, independently, hydrogen, methylsulfonyl,or nitro; and m=2-9.
 3. The compound in accordance with claim 2 whereinR³, R⁴ and R⁵ are, independently, hydrogen or nitro; and m=2-9.
 4. Thecompound in accordance with claim 2 wherein R³, R⁴ and R⁵ are,independently, hydrogen or methylsulfonyl; and m=0-9.
 5. A compositioncomprising an effective amount of the compound in accordance with claim1 in admixture with a optically acceptable polymer.
 6. A compositioncomprising an effective amount of the compound in accordance with claim1 attached to a optically acceptable polymer with a C₀₋₃₀spacer.
 7. Ause of a compound in accordance with claims 1-4 in an optical waveguideor an optical switch
 8. A use of a composition in accordance with claims5-6 in an optical waveguide or an optical switch.